E COT OXI COL OGY

POLYCYCLIC AROMATIC HYDROCARBON IN OYSTERS AND

SEDIMENT FROM THE YATSUSHIRO SEA JAPAN: COMPARISON
OOTENSTIAL RISKSAMONG PAHS, DIOXIN, DIOXIN-LIKE
COMPOUNDS IN BENTHIC ORGANISMS
CHARACTERISCTICS OF PAH
PAHs is a deverse class of organic compounds that
contain two or more fused aromatic (benzene)
rings that can be toxic to aquatic biota
It have been detected from air, water, sediment
and organisms
Accumulated chemical (Benthic and marine
mammals)


Benzo[a]pyrene (C20H12)
2-Methylnaphthalene

Source of PAH
Natural source (forest fires and volcano explosions)
Anthropogenic source (industrial activity, fossil fuel
combustion and waste inceneration)

Pyrogenic : Dominated by high MW PAH
Petrogenic : Dominated by low MW PAH
Phytogenic : from plant


Fate and Behaviour
Transform into other substances : photooxidation, hydrolysis,
biodegradation, mineralization
Cycling : adsorption, desorption, solubilization, volatilzation,
resuspention, and bioaccumation
http://gatewaypanel.review-examen.gc.ca/clf-nsi/dcmnt/rcmndtnsrprt/rcmndtnsrprtvlm2chp6-eng.html
TOXICITY OF PAH
PAHs have toxic to human and biota :
carcinogenetic and mutagenicity
The toxicity depend on species, route of exposure,
and molecular structure of PAH
LMW-PAHs : acutely toxic and noncarcinogenetic
HMW-PAHs : Not acutely toxic and carcinogenetic
The higher acute toxicity of LMW-PAHs is enhanced
by their water solubility
The lower acute toxicity of HMW-PAHs reflects their
low water solubility

Categories of PAH concentration in mussels and
sediments (Baumard et al, 1998)
Low (0-100 ng/g)
Moderate (100-1000 ng/g)
High (1000-5000 ng/g)
Very high (>5000 ng/g)
Canadian Interim Sediment Quality Guidelines (ISQGs)
and PEL (Probable Effect Level)
Effects Range Values developed by the US EPA as
sediment quality guidelines are used to protect against
the potential for adverse biological effects on organisms
:
Effect range low (ERL)
Effect range medium (ERM)

TOXIC EQUIVALET (TEQ)
Toxic Equivalents (TEQs) report the toxicity-weighted
masses of mixtures of PCDDs, PCDFs, and PCBs
Each compound is attributed a specific Toxic
Equivalency Factor (TEF). This factor indicates the
degree of toxicity compared to 2,3,7,8-TCDD, which is
given a reference value of 1.
The toxic equivalency of a mixture is defined by the sum
of the concentrations of individual compounds (C
i
)
multiplied by their relative toxicity (TEF):
TEQ = [C
i
] TEF
i

For each chemical the model uses comparative
measures from individual toxicity assays, known as
relative effect potency (REP)
Dioxin-Responsive Chemical-Activated LUciferase gene
eXpression assay (DR-CALUX) was applied to assess the
total toxic activity of the mixture of PAHs and related
compounds as well as dioxin-related compounds
THE OBJECTIVE
To understand the present level of PAH pollution
and its spatial distribution in the Yatsushiro sea by
analyzing bivalves and surface sediment collected
from polluted and reference sites
To estimate the potential source of PAH and the
toxicological effect by comparing the data with
SQGs
To analyse PCDD, PCDFs and PCB from polluted
and unpolluted areas of Yatsushiro Sea
To evaluate their toxicological contribution to
benthic organisms
METHODS
Oyster sampe taken from 18 sites in Yatsushiro sea
(2008)
Surface sediment sample collected from 42 sites in
Tanoura Bay dan references sites (2010)
Analytica Procedures
20 PAHs were analyzed
The chemicals were measured by gas chromatography (GC)

Statistics
PCA was conducted to investigated difference between PAH
mixtures were found in the oyster samples

Quality assurance
Deuterated surrogated standar were used to compesate for
PAH losses during the analytica method
Limit detection of PAH in oyster and sediment was 0,04 ng/g
and 0,02 ng/g
RESULTS AND DISCUSSION
The was mean conc. PAH in the oyster was 19 ng/g
PAH conc in station D (Tanoura Bays ) was ranging
57 350 ng/g
The PCA results show that station D and M was
grouped together. It indicate that there is existence
of a point source of PAH in this bay
The mean ration HM/LM-PAH in oyster was 0,52
(ranging from 0,26-1,36). It assume that the major
source of PAH in the Yatsushiro sea is Pyrogenic
PAH conc in St. E, F, H, O,Q and D-2 were moderate
(100-280 ng/g) while in D was high (1100-1700 ng/g)
RISK ASSESSMENT
Typical seafood consumption : 82,2 g/day
Dietary intake of BaP : 2,5-15,5 ng/kg BW /day
BaP No-observable adverse effect level (NOAEL) :
0,21 mg/kg/day
The acceptable daily intake (ADI) of BaP : 2,1
g/kg/day
Hazard ratio of BaP in oyster : 1,2 x10
-3
- 8 x 10
-3
PAH IN THE SEDIMENT OF TANOURA
BAY
The mean total PAH conc. In the sediment was 5240
ng/g.
The highest conc found in st. 26 (32700 ng/g)
The mean conc in Tanoura bay 20 times higher than
reference site
12 of 42 sites classified very high, 25 of 42 is high
The PAH decreased with increasing distance from
st. 26.
PCDD, PCDF, PCB IN TANOURA
SEDIMENT
These chemicals were found in 8 sites of tanoura
bay and two reference sites
The mean conc of PCDD : 1700 pg/g
The mean conc of PCDFs : 150 pg/g
The mean conc of PCBs : 110 pg/g
These values indicate an abstance of a point source of
these chemicals
The total TEQs ranged from 0,75-8,5 pg/g (below the
benchmark)




TOXIC POTENCIES OF PAH TO BENTHIC
More than 50 % of sediment samples exceeded ERL
values. St. 26 is higher than ERM
The adverse effect on benthic organisms may be
observed at more than 50 % of the sampling sites

TOXICOLOGICAL IMPLICATIONS
Total REP conc was ranged from 5,1-46 pg REP/g for
PCDDS, 0,52-23 pg REP/g for PCDFs, and 0,01-0,16
pg REP/g for PCBs
There were little difference in total REP of these
chemicals from polluted and reference site
PAH was found 11,500 pg REP tP/g in Tanoura Bay.
This value 30 times higher than reference site
PAH may pose more risk than PCDD, PCDF and PCB
to tidal organisms
COCLUSION
High PAH conc. Were detected in oyster and
sediment in Tanaoura bay indicating a existence of
a point source
Sediment samples of Tanoura Bay exceed ERL value
indicating that adverse effect in benthic in this area
No significant source of PCDD, PCDF and PCB in this
area
The total PAH REP was highest in Tanoura Bay